Shell catalyst, process for its preparation and use

Abstract

The present invention relates to a shell catalyst, a process for its preparation and also the use of the shell catalyst according to the invention.

1 . Shell catalyst comprising an open-pored catalyst support with a shell in which Ni and Cu and/or Pd and also in addition Mn and/or Mo are contained or in which Ni and also Mn and Mo are contained. 
     
     
         2 . Shell catalyst according to  claim 1 , characterized in that Ni and also Cu and/or Pd are present in the oxidation state 0. 
     
     
         3 . Shell catalyst according to  claim 1 , characterized in that Mn and/or Mo are present in oxide form. 
     
     
         4 . Shell catalyst according to  claim 1 , characterized in that Ni, Cu and Mn are contained in the shell. 
     
     
         5 . Shell catalyst according to  claim 4 , characterized in that the Ni/Cu atomic ratio of the shell catalyst is 0.5 to 30 and independently thereof the Ni/Mn atomic ratio 1 to 100. 
     
     
         6 . Shell catalyst according to  claim 1 , characterized in that Ni, Pd and Mo are contained in the shell. 
     
     
         7 . Shell catalyst according to  claim 6 , characterized in that the Ni/Pd atomic ratio of the shell catalyst is 10 to 500 and independently thereof the Ni/Mo atomic ratio 1 to 100. 
     
     
         8 . Shell catalyst according to  claim 1 , characterized in that the proportion of Ni in the shell catalyst is 5 wt.-% to 15 wt.-%. 
     
     
         9 . Shell catalyst according to  claim 1 , characterized in that the thickness of the shell is less than 2200 μm. 
     
     
         10 . Shell catalyst according to  claim 1 , characterized in that the catalyst support has a specific surface area of 40 m 2 /g to 160 m 2 /g. 
     
     
         11 . Shell catalyst according to  claim 1 , characterized in that the catalyst support has an integral pore volume according to BJH greater than/equal to 0.30 ml/g. 
     
     
         12 . Shell catalyst according to  claim 1 , characterized in that the catalyst support has an integral pore volume according to BJH of 0.3 ml/g to 1.2 ml/g. 
     
     
         13 . Shell catalyst according to  claim 1 , characterized in that at least 80% of the integral pore volume of the catalyst support is formed from mesopores and macropores. 
     
     
         14 . Shell catalyst according to  claim 1 , characterized in that the bulk density of the catalyst support is more than 0.30 g/ml. 
     
     
         15 . Shell catalyst according to  claim 1 , characterized in that the catalyst support has an average pore diameter of 8 nm to 50 nm. 
     
     
         16 . Shell catalyst according to  claim 1 , characterized in that the catalyst support has an acidity of 1 μval/g to 150 μval/g. 
     
     
         17 . Shell catalyst according to  claim 1 , characterized in that the catalyst support is formed as a shaped body. 
     
     
         18 . Shell catalyst according to  claim 17 , characterized in that the catalyst support is formed as a sphere with a diameter of 1 mm to 25 mm. 
     
     
         19 . Shell catalyst according to  claim 1 , characterized in that the catalyst support consists at least 50 wt.-% of SiO 2 , Al 2 O 3 , an aluminum silicate, ZrO 2 , TiO 2 , HfO 2 , MgO, niobium oxide or a natural sheet silicate or at least 50 wt.-% of a mixture of two or more of the above-mentioned materials. 
     
     
         20 . Shell catalyst according to  claim 1 , characterized in that the catalyst support consists at least 80 wt.-% of a natural sheet silicate. 
     
     
         21 . Shell catalyst according to  claim 1 , characterized in that the catalyst support consists at least 80 wt.-% of montmorillonite. 
     
     
         22 . Shell catalyst according to  claim 1 , characterized in that the catalyst has a hardness greater than/equal to 20 N. 
     
     
         23 . Shell catalyst according to  claim 1 , characterized in that the catalyst comprises at least one promoter selected from the group consisting of P, Na, K, Co and Mg. 
     
     
         24 . Process in which a catalyst support is sprayed with a solution in which a Ni compound and also a Cu compound and/or a Pd compound and also furthermore a Mn compound and/or a Mo compound are contained dissolved or in which a Ni compound and also a Mn compound and a Mo compound are contained dissolved. 
     
     
         25 . Process according to  claim 24 , comprising
 generating a fluidized bed of catalyst supports by means of a gas, whereas the catalyst supports move in the fluidized bed on an elliptical or toroidal path;   spraying of the catalyst supports moving in the fluidized bed on an elliptical or toroidal path with the solution.   
     
     
         26 . Process according to  claim 25 , characterized in that the catalyst supports move in the fluidized bed on a toroidal path. 
     
     
         27 . Process according to  claim 24 , characterized in that the process furthermore comprises
 drying of the catalyst supports sprayed with the solution.   
     
     
         28 . Process according to  claim 24 , characterized in that the process furthermore comprises
 calcining of the catalyst supports sprayed with the solution at a temperature at which the metal component of the metal compounds sprayed onto the catalyst supports is converted into an oxide form.   
     
     
         29 . Process according to  claim 24 , characterized in that the process furthermore comprises
 converting the metal component of one or more metal compounds sprayed onto the catalyst support into the oxidation state 0.   
     
     
         30 . Process according to  claim 24 , characterized in that a Ni compound, a Cu compound and a Mn compound are contained dissolved in the solution. 
     
     
         31 . Process according to  claim 24 , characterized in that a Ni compound, a Pd compound and a Mo compound are contained dissolved in the solution. 
     
     
         32 . Process according to  claim 24 , characterized in that the metal compounds contained in the solution are halogen-free metal compounds. 
     
     
         33 . Process according to  claim 24 , characterized in that the metal compounds contained in the solution are nitrate compounds of the respective metals. 
     
     
         34 . Process according to  claim 24 , characterized in that the solution is an aqueous solution. 
     
     
         35 . Process according to  claim 24 , characterized in that the process is carried out using a device which is set up to produce a fluidized bed of a particulate material by means of a gas, wherein the particles of the material move in the fluidized bed on an elliptical or toroidal path. 
     
     
         36 . Process according to  claim 35 , characterized in that the device comprises a process chamber with a bottom and a side wall, wherein the gas is fed into the process chamber with a horizontal movement component aligned radially outwards through the bottom of the process chamber whereas the bottom is preferably constructed of several overlapping annular guide plates laid one over the other between which annular slots are formed, in order to produce the catalyst support fluidized bed. 
     
     
         37 . Process according to  claim 36 , characterized in that a circumferential flow component is imposed on the gas fed into the process chamber. 
     
     
         38 . Process according to  claim 37 , characterized in that the circumferential flow component is imposed on the gas fed into the process chamber by means of guide elements which are arranged between the annular guide plates. 
     
     
         39 . Process according to  claim 37 , characterized in that the circumferential flow component is imposed on the gas fed into the process chamber by feeding additional gas through the bottom of the process chamber into the process chamber with a movement component aligned diagonally upwards. 
     
     
         40 . Process according to  claim 36 , characterized in that the catalyst supports moving in the fluidized bed on an elliptical or toroidal path are sprayed with the solution
 by means of an annular gap nozzle which atomizes a spray cloud which runs substantially parallel to the plane of the bottom.   
     
     
         41 . Process according to  claim 40 , characterized in that the annular gap nozzle is arranged centrally on the bottom and the mouth of the annular gap nozzle is embedded in the fluidized bed. 
     
     
         42 . Process according to  claim 40 , characterized in that a gas support cushion is produced on the underside of the spray cloud. 
     
     
         43 . Process according to  claim 25 , characterized in that the gas is selected from the group consisting of air, oxygen, nitrogen and the noble gases and also mixtures of the above gases. 
     
     
         44 . Process according to  claim 24 , characterized in that the process is carried out at a temperature greater than/equal to 60° C. 
     
     
         45 . Process according to  claim 36 , characterized in that the gas is enriched with the solvent of the solution before feeding into the process chamber. 
     
     
         46 . Use of a shell catalyst according to  claim 1  for the hydrogenation of aromatics, alkines, olefins, aldehydes and oxo products.